Active energy ray-curable composition, cured product and laminate

Abstract

To provide an active energy ray-curable composition capable of obtaining a cured coating film exhibiting good decorative properties in addition to scratch resistance and its application.SOLUTION: There is provided an active energy ray-curable composition comprising an urethane(meth)acrylate (A) and a (meth)acrylic polymer (B), wherein the urethane(meth)acrylate (A) has at least one structural unit (a1) selected from a group consisting of a structural unit based on 1,5-pentamethylene diisocyanate and a structural unit based on a derivative of 1,5-pentamethylene diisocyanate and a structural unit (a2) based on (meth)acrylate and the concentration of a (meth)acryloyl group of the urethane (meth)acrylate (A) is 5 mmol / g or more.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active energy ray curable composition, a cured product, and a laminate.

Background Art

[0002] Acrylic photocurable resins may be used to impart various performances to the surfaces of plastic films and plastic molded articles. For example, in the field of cosmetic containers and the like, a curable composition containing an acrylic photocurable resin may be applied to the surface of an ABS resin container to impart scratch resistance.

[0003] As a curable composition containing an acrylic photocurable resin, for example, in Patent Document 1, an active energy ray curable resin composition containing a polyfunctional glycerin (meth) acrylate (A), a (meth) acrylic monomer (B), a specific urethane (meth) acrylate (C), a (co) polymer (D) of a vinyl monomer, and a photopolymerization initiator (E) has been proposed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, in a cured coating film composed of a cured product of a conventional curable composition containing an acrylic photocurable resin, although the scratch resistance is good, it is difficult to improve its appearance and texture by various treatments such as painting, plating, printing, and coloring. That is, there is room for improvement in decorativeness.

[0006] The present invention provides an active energy ray curable composition capable of obtaining a cured coating film that exhibits good decorativeness in addition to scratch resistance.

Means for Solving the Problem

[0007] The present invention has the following aspects. [1] An active energy ray-curable composition containing urethane (meth)acrylate (A) and (meth)acrylic polymer (B), wherein the urethane (meth)acrylate (A) has at least one structural unit (a1) selected from the group consisting of a structural unit based on 1,5-pentamethylene diisocyanate and a structural unit based on a derivative of 1,5-pentamethylene diisocyanate, and a structural unit (a2) based on (meth)acrylate, and the concentration of the (meth)acryloyl group in the urethane (meth)acrylate (A) is 5 mmol / g or more. [2] The active energy ray-curable composition according to [1], wherein the content rate of the carbon atoms derived from a living organism in the structural unit (a1) is 50% by mass or more. [3] The active energy ray-curable composition according to [1] or [2], further containing glycerin (meth)acrylate (C) derived from biomass. [4] The active energy ray-curable composition according to [3], wherein the glycerin (meth)acrylate (C) is glycerin di(meth)acrylate (C1). [5] The active energy ray-curable composition according to [3] or [4], wherein the ratio of the (meth)acrylic polymer (B) is 30 parts by mass or more with respect to 100 parts by mass of the glycerin (meth)acrylate (C). [6] The active energy ray-curable composition according to any one of [1] to [5], further containing urethane (meth)acrylate (D) having a structural unit based on the following compound (d1), a structural unit based on the following compound (d2), and a structural unit based on the following compound (d3). Compound (d1): An isocyanate compound having at least two isocyanate groups (however, 1,5-pentamethylene diisocyanate is excluded). Compound (d2): At least one polyol selected from the group consisting of polyether polyol, polyester polyol, and polycarbonate polyol. Compound (d3): A compound having a hydroxyl group and a (meth)acryloyl group. [7] The active energy ray-curable composition according to [6], wherein the compound (d3) is a compound other than glycerin (meth)acrylate. [8] A cured product of the active energy ray-curable composition according to any one of [1] to [7]. [9] The cured product according to [8], wherein the content of carbon atoms derived from a living organism is 10% by mass or more.

[10] Having a substrate and a cured coating film provided on the surface of the substrate, The laminate, wherein the cured coating film is composed of the cured product according to [8] or [9]. [Advantages of the Invention]

[0008] According to the active energy ray-curable composition of the present invention, a cured coating film that exhibits good decorativeness in addition to scratch resistance can be obtained. The cured coating film of the present invention exhibits good decorativeness in addition to scratch resistance. The laminate of the present invention has a cured coating film that exhibits good decorativeness in addition to scratch resistance. [Embodiments for Carrying Out the Invention]

[0009] The meanings of the terms are as follows. "Monomer" and "monomer" mean a compound having a polymerizable carbon-carbon double bond. "(Meth)acrylate" is a general term for "acrylate" and "methacrylate". "(Meth)acrylic acid" is a general term for "acrylic acid" and "methacrylic acid". "~" indicating a numerical range means including the numerical values described before and after it as a lower limit value and an upper limit value. The numerical ranges, upper limit values, and lower limit values of the physical property values disclosed in this specification can be arbitrarily combined to form a new numerical range.

[0010] [Active Energy Ray-Curable Composition] The active energy ray-curable composition of the present invention contains a urethane (meth)acrylate (A) described below and a (meth)acrylic polymer (B) described below.

[0011] In addition to the urethane (meth)acrylate (A) and the (meth)acrylic polymer (B), the active energy ray-curable composition of the present invention may further contain a glycerin (meth)acrylate (C) described below and a urethane (meth)acrylate (D) described below.

[0012] In addition to the urethane (meth)acrylate (A), the (meth)acrylic polymer (B), the glycerin (meth)acrylate (C), and the urethane (meth)acrylate (D), the active energy ray-curable composition of the present invention may further contain a photopolymerization initiator (E).

[0013] In addition to the urethane (meth)acrylate (A), the (meth)acrylic polymer (B), the glycerin (meth)acrylate (C), the urethane (meth)acrylate (D), and the photopolymerization initiator (E), the active energy ray-curable composition of the present invention may further contain other components.

[0014] Hereinafter, several embodiments and each component will be described in detail. However, the following description relates to representative examples, and the present invention is not limited to the following description.

[0015] (Urethane (meth)acrylate (A)) The urethane (meth)acrylate (A) has a structural unit (a1) and a structural unit (a2) described below.

[0016] The structural unit (a1) is at least one structural unit selected from the group consisting of a structural unit based on 1,5-pentamethylene diisocyanate and a structural unit based on a derivative of 1,5-pentamethylene diisocyanate.

[0017] Examples of derivatives of 1,5-pentamethylene diisocyanate include, for example, trimer compounds or higher multimer compounds of 1,5-pentamethylene diisocyanate, allophanate-type polyisocyanates, biuret-type polyisocyanates, adduct-type polyisocyanates, and water-dispersible polyisocyanates.

[0018] Although not particularly limited, 1,5-pentamethylene diisocyanate and its derivatives may be derived from biomass. The content of carbon atoms derived from organisms in the structural unit (a1) is preferably 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more. The content of carbon atoms derived from organisms is a value measured in accordance with ASTM D6866-04.

[0019] In addition to the structural unit (a1), the urethane (meth) acrylate (A) may further have a structural unit based on an isocyanate and its derivative other than 1,5-pentamethylene diisocyanate.

[0020] Examples of other isocyanates include, for example, aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, trimer compounds or higher multimer compounds of these polyisocyanates, allophanate-type polyisocyanates, biuret-type polyisocyanates, adduct-type polyisocyanates, and water-dispersible polyisocyanates.

[0021] Examples of aromatic polyisocyanates include, for example, tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate. Examples of the aliphatic polyisocyanate include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate. Examples of the alicyclic polyisocyanate include hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, and norbornene diisocyanate.

[0022] The structural unit (a2) is a structural unit based on a hydroxyl group-containing (meth)acrylate. The hydroxyl group-containing (meth)acrylate has at least one (meth)acryloyl group and at least one hydroxyl group. The ethylenically unsaturated group of the hydroxyl group-containing (meth)acrylate may be one, two, or three or more.

[0023] Examples of the hydroxyl group-containing (meth)acrylate having one ethylenically unsaturated group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 6-hydroxyhexyl (meth)acrylate, 2-hydroxyethyl acryloyl phosphate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth)acrylate, dipropylene glycol (meth)acrylate, fatty acid-modified glycidyl (meth)acrylate, polyethylene glycol mono (meth)acrylate, polypropylene glycol mono (meth)acrylate, and 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate.

[0024] Examples of the hydroxyl group-containing (meth)acrylate having two ethylenically unsaturated groups include, for example, -hydroxy-3-acryloyl-oxypropyl methacrylate.

[0025] Examples of the hydroxyl group-containing (meth)acrylate having three or more ethylenically unsaturated groups include pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol penta(meth)acrylate, and ethylene oxide-modified dipentaerythritol penta(meth)acrylate.

[0026] The hydroxyl group-containing (meth)acrylate may be used alone or in combination of two or more.

[0027] The concentration of the (meth)acryloyl group in the urethane (meth)acrylate (A) is 5 mmol / g or more, preferably 6 mmol / g or more, more preferably 7 mmol / g or more, and even more preferably 8 mmol / g or more. When the concentration of the (meth)acryloyl group in the urethane (meth)acrylate (A) is at or above the lower limit value, a coating film with good scratch resistance is easily obtained.

[0028] The concentration of the (meth)acryloyl group in the urethane (meth)acrylate (A) is preferably 14 mmol / g or less, more preferably 12 mmol / g or less, and even more preferably 10 mmol / g or less. When the concentration of the (meth)acryloyl group in the urethane (meth)acrylate (A) is at or below the upper limit value, a coating film with good decorativeness is easily obtained.

[0029] The concentration of the (meth)acryloyl group in the urethane (meth)acrylate (A) is a numerical value calculated from the ratio of the acryloyl group [CH2=CH-C(=O)-] and the methacryloyl group [CH2=C(CH3)-C(=O)-] in its molecular structural formula. The concentration M of the (meth)acryloyl group in the urethane (meth)acrylate (A) can be determined by the following formula (1). M = (N × 1000 / P) × (Q / 100) ··· (1) In the formula, N is the number of (meth)acryloyl groups of the hydroxyl group-containing (meth)acrylate that provides the structural unit (a2), P is the molar mass (g / mol) of the hydroxyl group-containing (meth)acrylate that provides the structural unit (a2), and Q is the proportion (mass %) of the structural unit (a2) in all the structural units of the urethane (meth)acrylate (A).

[0030] The method for producing the urethane (meth)acrylate (A) is not particularly limited. For example, the urethane (meth)acrylate (A) can be obtained by charging a polyisocyanate and a hydroxyl group-containing (meth)acrylate into a reactor all at once or dropwise and reacting them. In one example, the reaction is terminated when the residual isocyanate group content in the reaction system becomes 0.5 mass % or less, whereby the urethane (meth)acrylate (A) can be obtained.

[0031] In the production of the urethane (meth)acrylate (A), it is preferable to use a catalyst for the purpose of accelerating the reaction. Examples of such catalysts include organometallic compounds, metal salts, amine-based catalysts, bismuth-based catalysts, zirconium-based catalysts, and zinc 2-ethylhexanoate / zirconium tetraacetylacetonate. The catalyst may be used alone or in combination of two or more.

[0032] Examples of the organometallic compounds include dibutyltin dilaurate, trimethyltin hydroxide, tetra-n-butyltin, and tin octylate.

[0033] Examples of the metal salts include zinc octenoate, tin octenoate, cobalt naphthenate, stannous chloride, and stannic chloride.

[0034] Examples of the amine-based catalysts include triethylamine, benzyldiethylamine, 1,4-diazabicyclo[2,2,2]octane, 1,8-diazabicyclo[5,4,0]undecene, N,N,N’,N’-tetramethyl-1,3-butanediamine, and N-ethylmorpholine.

[0035] As the bismuth-based catalyst, for example, in addition to bismuth nitrate, bismuth bromide, bismuth iodide, bismuth sulfide, etc., there are also organobismuth compounds such as dibutylbismuth dilaurate, dioctyldibismuth dilaurate, and bismuth salts of organic acids such as bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth isodecanoate, bismuth neodecanoate, bismuth laurate, bismuth maleate, bismuth stearate, bismuth oleate, bismuth linoleate, bismuth acetate, bismuth bisneodecanoate, bismuth disalicylate, bismuth digallate, etc.

[0036] As the zirconium-based catalyst, for example, inorganic zirconium, organic zirconium, and zirconium alone can be mentioned. Among them, dibutyltin dilaurate and 1,8-diazabicyclo[5,4,0]undecene are preferred.

[0037] In the production of urethane (meth)acrylate (A), an organic solvent having no functional group reactive with an isocyanate group can be used. For example, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone and methyl isobutyl ketone, and aromatic organic solvents such as toluene and xylene can be used. However, from the viewpoint of reducing environmental load, it is preferable to carry out the reaction without a solvent.

[0038] The reaction temperature can be 30 to 90 °C, preferably 40 to 80 °C. The reaction time can be 2 to 10 hours, preferably 3 to 8 hours.

[0039] ((Meth)acrylic polymer (B)) (Meth)acrylic polymer (B) may be a homopolymer or a copolymer of (meth)acrylate. (Meth)acrylate is a monomer having at least one (meth)acryloyl group. The number of (meth)acryloyl groups may be one, two, or three or more. Also, the (meth)acrylate referred to herein may be epoxy poly(meth)acrylate or polyester poly(meth)acrylate. However, (meth)acrylic polymer (B) is a different component separate from urethane (meth)acrylate (A).

[0040] (Meth)acrylate in (meth)acrylic polymer (B) is not particularly limited, and examples thereof include the following compounds.

[0041] Examples of monomers having one (meth)acryloyl group include (meth)acrylates having a hydrocarbon group such as 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, 2-isobutyl-2-methyl acrylate, etc.; (Meth)acrylates having a ring skeleton such as tetrahydrofurfuryl (meth)acrylate, 2-ethyl-2-methyl-1,3-dioxolan-4-yl-methyl (meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, adamantyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, phenyloxyethyl (meth)acrylate, phenyloxydiethylene glycol (meth)acrylate, ethylene oxide-modified cresol (meth)acrylate, nonylphenyloxyethyl (meth)acrylate, paracumylphenyloxyethyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl-oxyethyl (meth)acrylate, cyclohexyloxyethyl (meth)acrylate, t-butylcyclohexyloxyethyl (meth)acrylate, benzyloxyethyl (meth)acrylate, isobornyloxyethyl (meth)acrylate, norbornyloxyethyl (meth)acrylate, adamantyloxyethyl (meth)acrylate; (Meth)acrylates having an alkoxy group-containing hydrocarbon skeleton such as 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxytriethylene glycol (meth)acrylate, methoxydipropylene glycol (meth)acrylate, methoxytripropylene glycol (meth)acrylate, methoxydibutylene glycol (meth)acrylate, methoxytributylene glycol (meth)acrylate, ethoxydiethylene glycol (meth)acrylate, ethoxytriethylene glycol (meth)acrylate, ethoxydipropylene glycol (meth)acrylate, ethoxytripropylene glycol (meth)acrylate, ethoxydibutylene glycol (meth)acrylate, ethoxytributylene glycol (meth)acrylate, butoxyethyl (meth)acrylate; (Meth)acrylamides such as dimethylacrylamide; (Meth)acrylamides having a heterocyclic ring such as acryloylmorpholine can be mentioned.

[0042] Examples of the monomer having two (meth)acryloyl groups include di(meth)acrylates having a ring skeleton such as tricyclodecane dimethanol di(meth)acrylate, cyclohexane dimethanol di(meth)acrylate, hydrogenated bisphenol A di(meth)acrylate, and bisphenoxytetrafluoroethane ethanol di(meth)acrylate; Di(meth)acrylates having an isocyanuric acid skeleton such as bis(2-acryloyloxyethyl)-2-hydroxyethyl isocyanurate; Di(meth)acrylates having a trimethylolpropane skeleton such as neopentyl glycol-modified trimethylolpropane di(meth)acrylate; Di(meth)acrylates having a hydrocarbon skeleton such as 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 2,4-diethyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 2-methyl-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,11-undecanediol di(meth)acrylate, 1,12-dodecanediol di(meth)acrylate, 1,13-tridecanediol di(meth)acrylate, 1,14-tetradecanediol di(meth)acrylate; Examples of the di(meth)acrylate having a polyether skeleton include tripropylene glycol di(meth)acrylate and polybutylene glycol di(meth)acrylate.

[0043] Examples of the monomer having three (meth)acryloyl groups include tri(meth)acrylates having a trimethylolpropane skeleton such as trimethylolpropane tri(meth)acrylate and tris(ethoxylated)trimethylolpropane tri(meth)acrylate; Examples of the tri(meth)acrylate having an isocyanuric acid skeleton include tris(2-acryloyloxyethyl)isocyanurate.

[0044] Examples of the monomer having four or more (meth)acryloyl groups include poly(meth)acrylates having a trimethylolpropane skeleton such as ditrimethylolpropane tetra(meth)acrylate.

[0045] Examples of the epoxy poly(meth)acrylate include bisphenol type epoxy di(meth)acrylate and novolac type epoxy di(meth)acrylate.

[0046] Examples of the polyester poly(meth)acrylate include compounds obtained by the reaction of a polyester polyol obtained by an esterification reaction of a polybasic acid such as phthalic acid, succinic acid, hexahydrophthalic acid, tetrahydrophthalic acid, terephthalic acid, azelaic acid, adipic acid, etc. and a polyol such as ethylene glycol, hexanediol, polyethylene glycol, polytetramethylene glycol, etc. with (meth)acrylic acid or its derivative.

[0047] (Glycerin (meth)acrylate (C)) The active energy ray-curable composition preferably further contains biomass-derived glycerin (meth)acrylate (C) in that the scratch resistance and substrate adhesion are further improved. Examples of the glycerin (meth)acrylate (C) include glycerin di(meth)acrylate, glycerin tri(meth)acrylate, ethylene oxide-modified glycerin di(meth)acrylate, ethylene oxide-modified glycerin tri(meth)acrylate, propylene-modified glycerin di(meth)acrylate, propylene-modified glycerin tri(meth)acrylate, and polyfunctional polyglycerin (meth)acrylate. Among them, as the glycerin (meth)acrylate (C), glycerin di(meth)acrylate (C1) is preferable.

[0048] When the active energy ray-curable composition contains glycerin (meth)acrylate (C), the proportion of the (meth)acrylic polymer (B) is preferably 30 parts by mass or more, more preferably 30 parts by mass or more and 90 parts by mass or less, still more preferably 30 parts by mass or more and 70 parts by mass or less, with respect to 100 parts by mass of the glycerin (meth)acrylate (C). If the proportion of the (meth)acrylic polymer (B) is at least the above lower limit with respect to the glycerin (meth)acrylate (C), the decorativeness is likely to be improved.

[0049] (Urethane (meth)acrylate (D)) The active energy ray-curable composition preferably further contains urethane (meth)acrylate (D) in that the decorativeness is further improved. The urethane (meth)acrylate (D) has a structural unit based on the following compound (d1), a structural unit based on the following compound (d2), and a structural unit based on the following compound (d3).

[0050] Compound (d1): An isocyanate compound having at least two isocyanate groups (however, 1,5-pentamethylene diisocyanate is excluded). Compound (d2): At least one polyol selected from the group consisting of polyether polyol, polyester polyol, and polycarbonate polyol. Compound (d3): A compound having a hydroxyl group and a (meth)acryloyl group.

[0051] Compound (d1) is an isocyanate compound having at least two isocyanate groups. Compound (d1) contributes to the flexibility of the coating film. Compound (d1) is not particularly limited. For example, aromatic polyisocyanates such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate; Aliphatic polyisocyanates such as ethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, lysine triisocyanate; Alicyclic polyisocyanates such as isophorone diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, methylcyclohexylene diisocyanate; Arylaliphatic polyisocyanates such as xylylene diisocyanate, tetramethylxylylene diisocyanate; Examples include biuret bodies and allophanate bodies of the above polyisocyanates. Compound (d1) may be used alone or in combination of two or more.

[0052] Among these, since they can impart excellent toughness to the coating film, as the compound (d1), aliphatic backbone diisocyanates such as 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, bis(4-isocyanatocyclohexyl)methane, 1,2-hydrogenated xylylene diisocyanate, 1,4-hydrogenated xylylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, norbornane diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate are preferred.

[0053] The compound (d2) is at least one polyol selected from the group consisting of polyether polyol, polyester polyol, and polycarbonate polyol. The compound (d2) contributes to the anti-blocking property and smoothness of the coating film. Examples of the compound (d2) include the following compound (d21) and compound (d22). The compound (d2) may be used alone or in combination of two or more.

[0054] The compound (d21) is a polyester polyol obtained from an aliphatic polycarboxylic acid having 2 to 22 carbon atoms and a polyhydric alcohol. Examples of the aliphatic polycarboxylic acid having 2 to 22 carbon atoms used as a raw material of the compound (d21) include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, aconitic acid, trimesic acid, and butanetetracarboxylic acid. Among these, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred from the viewpoint of easy control of the molecular weight of the polyester polyol. Among these, sebacic acid is preferred from the viewpoint of compatibility.

[0055] Examples of the polyol used as a raw material for the compound (d21) include neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,6 - hexanediol, 1,4 - butanediol, 1,9 - nonanediol, 1,10 - decanediol, 3 - methylpentanediol, 2,4 - diethylpentanediol, tricyclodecane dimethanol, 1,4 - cyclohexanedimethanol, 1,2 - cyclohexanedimethanol, 1,3 - cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A, trimethylolpropane, and pentaerythritol. Examples of the polyester polyol used as the compound (d21) include sebacic acid polyester polyol, adipic acid polyester polyol, terephthalic acid polyester polyol, and isophthalic acid polyester polyol. Among these, sebacic acid polyester polyol is preferred from the viewpoint of the moisture resistance of the coating film.

[0056] When the compound (d21) is used as a raw material for urethane (meth) acrylate (D), the urethane (meth) acrylate (D) contains, as a structure derived from the compound (d21), a structure obtained by removing at least two hydroxyl groups from a polyester polyol obtained from an aliphatic polycarboxylic acid having 2 to 22 carbon atoms and a polyhydric alcohol.

[0057] The compound (d22) is a polyether polyol having 2 to 5 carbon atoms in the repeating unit. Examples of the polyether polyol having 2 to 5 carbon atoms in the repeating unit used as the compound (d22) include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Among these, polytetramethylene glycol is preferred from the viewpoint of the moisture resistance of the coating film.

[0058] In the synthesis of urethane (meth) acrylate (D), in addition to compounds (d21) and (d22) as the raw material polyol, other polyols can also be used in combination. Examples of other polyols include polyols such as neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,6 - hexanediol, 1,4 - butanediol, 1,9 - nonanediol, 1,10 - decanediol, 3 - methylpentanediol, 2,4 - diethylpentanediol, tricyclodecane dimethanol, 1,4 - cyclohexanedimethanol, 1,2 - cyclohexanedimethanol, 1,3 - cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A, trimethylolpropane, pentaerythritol; Polyether - modified polyols obtained by adding alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide to the above - mentioned polyhydric alcohols; Polycaprolactone polyols obtained by the reaction of the above - mentioned polyhydric alcohols with lactones such as ε - caprolactone, γ - butyrolactone, γ - valerolactone, and δ - valerolactone; Caprolactone - modified polyester polyols obtained by the reaction of the above - mentioned polyhydric alcohols and polybasic acids with lactones such as ε - caprolactone, γ - butyrolactone, γ - valerolactone, and δ - valerolactone; Polycarbonate diols obtained by transesterification reaction of diols such as 1,6 - hexanediol, 3 - methylpentanediol, 2,4 - diethylpentanediol, trimethylhexanediol, 1,4 - butanediol, 1,5 - pentanediol, 1,4 - cyclohexanediol, etc. and carbonates such as ethylene carbonate, dimethyl carbonate, diethyl carbonate, di - n - propyl carbonate, diisopropyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, etc.; polybutadiene glycol. Among these, polyols such as neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,6 - hexanediol, 1,4 - butanediol, 1,9 - nonanediol, 1,10 - decanediol, 3 - methylpentanediol, 2,4 - diethylpentanediol, tricyclodecane dimethanol, 1,4 - cyclohexanedimethanol, 1,2 - cyclohexanedimethanol, 1,3 - cyclohexanedimethanol, cyclohexanediol, hydrogenated bisphenol A, trimethylolpropane, pentaerythritol, etc. are preferred because the curability of this composition is good.

[0059] The molecular weight of compound (d21) is preferably 500 or more and less than 3000. The molecular weight of compound (d22) is preferably 500 or more and less than 3000. If the molecular weight is at least the lower limit, the moisture resistance of the coating film will be good, and if it is at most the upper limit, the appearance of the coating film will be good.

[0060] Compound (d3) is a compound having a hydroxyl group and a (meth)acryloyl group. Compound (d3) may be any compound as long as its hydroxyl group can form a urethane bond with the isocyanate group of compound (d1) or an intermediate compound having an isocyanate group obtained from compound (d1) and introduce a (meth)acryloyloxy group into urethane (meth)acrylate (D).

[0061] Examples of the compound (d3) include (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and caprolactone adducts of these (meth)acrylates. Among these, in terms of compatibility with acrylic polymers, the compound (d3) is preferably a compound other than glycerin (meth)acrylate.

[0062] In terms of obtaining a urethane (meth)acrylate (D) with low viscosity, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate are preferred. For the synthesis of urethane (meth)acrylate (D), one kind of the compound (d3) may be used alone, or two or more kinds of the compounds (d3) may be used in combination.

[0063] Urethane (meth)acrylate (D) can be produced by a conventionally known synthesis method. For example, 2 mol of the compound (d1) is charged into a flask, and a known catalyst such as dibutyltin dilaurate is further mixed. While maintaining the temperature in the flask at 40 to 80°C, 1 mol of the compound (d2) is dropped using a dropping funnel to obtain a urethane prepolymer having an isocyanate group at the terminal. Then, 2 mol of the compound (d3) having a hydroxyl group equivalent to the isocyanate group remaining at the terminal of the obtained urethane prepolymer is dropped, and the addition reaction between the isocyanate group of the urethane prepolymer and the hydroxyl group of the compound (d3) is carried out at 60 to 85°C to synthesize urethane (meth)acrylate (D). The end point of the reaction can be determined by quantifying the remaining isocyanate group. The reaction rate at the end point is preferably 97% or more, more preferably 99% or more.

[0064] (Photoinitiator (E)) Examples of the photopolymerization initiator (E) include benzophenone-type photopolymerization initiators, anthraquinone-type photopolymerization initiators, alkylphenone-type photopolymerization initiators, thioxanthone-type photopolymerization initiators, acylphosphine oxide-type photopolymerization initiators, and phenylglyoxylate-type photopolymerization initiators.

[0065] Examples of the photopolymerization initiator (E) include benzophenone-type such as benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, methyl orthobenzoylbenzoate, 4-phenylbenzophenone; anthraquinone-type such as t-butylanthraquinone, 2-ethylanthraquinone; alkylphenone-type such as 2-hydroxy-2-methyl-1-phenylpropan-1-one, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone}, benzyldimethylketal, 1-hydroxycyclohexylphenylketone, benzoin methyl ether, 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one; thioxanthone-type such as 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, diethylthioxanthone, isopropylthioxanthone; acylphosphine oxide-type such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; and phenylglyoxylate-type photopolymerization initiators such as phenylglyoxylic acid methyl ester. Among these, from the viewpoint of touch dryness, benzophenone, 2-ethylanthraquinone, 1-hydroxycyclohexylphenylketone, and 2,2-dimethoxy-1,2-diphenylethane-1-one are preferable. The photoinitiator (E) may be used alone or in combination of two or more kinds.

[0066] (Other components) The active energy ray-curable composition may further contain other components as needed. Examples of the other components include photosensitizers, organic solvents, leveling agents, defoaming agents, anti-settling agents, lubricants, abrasives, rust preventives, antistatic agents, light stabilizers, ultraviolet absorbers, and polymerization inhibitors. Also, within a range that does not interfere with the effects of the present invention, resins such as alkyd resins may be blended in the active energy ray-curable composition.

[0067] Examples of the photosensitizer include methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate, and 4-dimethylaminoacetophenone.

[0068] Examples of the organic solvent include ketone compounds such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester compounds such as methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, and methoxyethyl acetate; ether compounds such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and dioxane; aromatic compounds such as toluene and xylene; aliphatic compounds such as pentane, hexane, and petroleum naphtha; alcohol compounds such as isopropyl alcohol, isobutanol, and n-butanol; propylene glycol compounds such as 1-methoxypropanol and 1-methoxypropyl acetate.

[0069] (Composition) The proportion of urethane (meth)acrylate (A) is preferably 1 to 70% by mass, more preferably 1 to 60% by mass, and even more preferably 1 to 50% by mass of the total amount of the active energy ray-curable composition. If the content of urethane (meth)acrylate (A) is at least the lower limit value within the above numerical range, the scratch resistance is more likely to be further improved. If the content of urethane (meth)acrylate (A) is at most the upper limit value within the above numerical range, the decorativeness is more likely to be further improved.

[0070] The proportion of (meth)acrylic polymer (B) is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably 5 to 40% by mass of the total amount of the active energy ray-curable composition. If the content of (meth)acrylic polymer (B) is at least the lower limit value within the above numerical range, the decorativeness is more likely to be further improved. If the content of (meth)acrylic polymer (B) is at most the upper limit value within the above numerical range, the scratch resistance is more likely to be further improved.

[0071] When the active energy ray-curable composition contains glycerin (meth)acrylate (C), the proportion of glycerin (meth)acrylate (C) is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably 1 to 30% by mass of the total amount of the active energy ray-curable composition. If the content of glycerin (meth)acrylate (C) is at least the lower limit value within the above numerical range, the scratch resistance and adhesion are more likely to be further improved. If the content of glycerin (meth)acrylate (C) is at most the upper limit value within the above numerical range, the decorativeness is more likely to be further improved.

[0072] When the active energy ray-curable composition contains urethane (meth)acrylate (D), the proportion of urethane (meth)acrylate (D) is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, and even more preferably 1 to 30% by mass of the total amount of the active energy ray-curable composition. If the content of urethane (meth)acrylate (D) is at least the lower limit value within the above numerical range, the decorativeness is more likely to be further improved. If the content of urethane (meth)acrylate (D) is at most the upper limit value within the above numerical range, the adhesion is more likely to be further improved.

[0073] When the active energy ray curable composition contains a photoinitiator (E), the proportion of the photoinitiator (E) is preferably 1 to 10% by mass, more preferably 1 to 8% by mass, and even more preferably 1 to 5% by mass of the total amount of the active energy ray curable composition. If the content of the photoinitiator (E) is at least the lower limit value within the above numerical range, the scratch resistance is more likely to be further improved. If the content of the photoinitiator (E) is at most the upper limit value within the above numerical range, the decorativeness is more likely to be further improved.

[0074] (Cured product) By irradiating the active energy ray curable composition with active energy rays, a cured product of the active energy ray curable composition can be obtained. The active energy rays are not particularly limited, and examples thereof include light rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, and visible light rays, and ionizing radiations such as X-rays, α-rays, β-rays, γ-rays, electron beams, proton beams, and neutron beams. For example, when irradiating with ultraviolet rays using a high-pressure mercury lamp, the energy amount is 50 to 5000 mJ / cm 2 is preferable, and 100 to 2000 mJ / cm 2 is more preferable.

[0075] The content rate of the carbon atoms derived from organisms in the cured product is preferably 10% by mass or more, more preferably 12% by mass or more, and even more preferably 15% by mass or more. The content rate of the carbon atoms derived from organisms in the cured product is a value obtained by the following formula. (Content rate of carbon atoms derived from organisms) (%) = ((Ratio of carbon atoms derived from plants) / ((Ratio of carbon atoms derived from plants) + (Ratio of carbon atoms derived from petroleum)) × 100

[0076] [Laminated body] The laminated body of the present invention has a substrate and a cured coating film provided on the surface of the substrate, and the cured coating film is composed of a cured product of the active energy ray curable composition of the present invention.

[0077] The base material is not particularly limited. For example, molding base materials and films made of synthetic resins such as ABS resin, AES resin, acrylic resin, polycarbonate resin, polyurethane resin, polystyrene resin, polyolefins such as polypropylene and polyethylene, and polyesters such as PET and PBT, painted formed steel sheets, stainless steel, aluminum, brass, chromium-plated steel materials, and glass can be mentioned. Among these, resin base materials such as ABS resin, AES resin, polycarbonate, acrylic resin, and polystyrene are preferred.

[0078] For example, after applying an active energy ray curable composition to the surface of the base material, the laminate can be obtained by irradiating active energy rays. The use of the laminate is not particularly limited. For example, a plant-derived hard coat material used after decorating the cured coating film obtained after applying it to plastic base materials such as ABS, polycarbonate, acrylic, and PET can be mentioned.

Examples

[0079] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following description.

[0080] [Raw materials used] (Synthesis of urethane (meth) acrylate (A-1)) Into a flask equipped with an internal thermometer, a stirrer, and a condenser, 150.59 g (0.977 mol) of pentamethylene diisocyanate, 821.03 g (1.74 mol) of an acrylic acid adduct of pentaerythritol (a21) [hydroxyl value: 118.9 mgKOH / g], 28.37 g (0.244 mol) of 2-hydroxyethyl acrylate (a22), 0.80 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst were added, and the reaction was carried out at 60 °C. The reaction was terminated when the residual isocyanate group became 0.1% or less, and a composition containing urethane (meth) acrylate (A-1) was obtained (mass average molecular weight: 1,200, solution viscosity: 810 mPa·s / 60 °C).

[0081] (Synthesis of urethane (meth)acrylate (A-2)) Into a flask equipped with an internal thermometer, a stirrer, and a condenser, 92.87 g (0.603 mol) of pentamethylene diisocyanate, 751.61 g (0.603 mol) of acrylic acid adduct (a23) of dipentaerythritol [hydroxyl value: 45.0 mg KOH / g], 155.52 g (0.621 mol) of acrylic acid adduct (a24) of glycerin [hydroxyl value: 224.0 mg KOH / g], 0.80 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst were added, and the reaction was carried out at 60°C. The reaction was terminated when the residual isocyanate group became 0.1% or less, and a composition containing urethane (meth)acrylate (A-2) was obtained (weight average molecular weight: 1,800, solution viscosity: 930 mPa·s / 60°C).

[0082] (Synthesis of urethane (meth)acrylate (A-3)) Into a flask equipped with an internal thermometer, a stirrer, and a condenser, 174.84 g (1.135 mol) of pentamethylene diisocyanate, 532.38 g (1.135 mol) of acrylic acid adduct (a21) of pentaerythritol [hydroxyl value: 119.6 mg KOH / g], 292.78 g (1.169 mol) of acrylic acid adduct (a24) of glycerin [hydroxyl value: 224.0 mg KOH / g], 0.80 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst were added, and the reaction was carried out at 60°C. The reaction was terminated when the residual isocyanate group became 0.1% or less, and a composition containing urethane (meth)acrylate (A-4) was obtained (weight average molecular weight: 1,200, solution viscosity: 680 mPa·s / 60°C).

[0083] (Synthesis of urethane (meth)acrylate (A-4)) Into a flask equipped with an internal thermometer, a stirrer, and a cooling tube, 202.19 g (1.312 mol) of pentamethylene diisocyanate, 640.85 g (1.312 mol) of an acrylic acid adduct (a21) of pentaerythritol [hydroxyl value: 118.9 mg KOH / g], 156.96 g (1.352 mol) of 2-hydroxyethyl acrylate (a22), 0.80 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst were added, and the reaction was carried out at 60°C. The reaction was terminated when the residual isocyanate group became 0.1% or less, and a composition containing urethane (meth)acrylate (A-7) was obtained (weight average molecular weight: 900, solution viscosity: 360 mPa·s / 60°C).

[0084] (Synthesis of urethane (meth)acrylate (A-5)) Into a flask equipped with an internal thermometer, a stirrer, and a cooling tube, 395.26 g (2.565 mol) of pentamethylene diisocyanate, 604.74 g (5.208 mol) of 2-hydroxyethyl acrylate (a22), 0.80 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst were added, and the reaction was carried out at 60°C. The reaction was terminated when the residual isocyanate group became 0.1% or less, and a composition containing a urethane acrylate compound was obtained (weight average molecular weight: 600, solution viscosity: 130 mPa·s / 60°C).

[0085] (Synthesis of urethane (meth)acrylate (A-6)) Into a flask equipped with an internal thermometer, a stirrer, and a cooling tube, 232.54 g (1.509 mol) of pentamethylene diisocyanate, 767.46 g (3.063 mol) of an acrylic acid adduct (a24) of glycerin [hydroxyl value: 224.0 mg KOH / g], 0.80 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst were added, and the reaction was carried out at 60°C. The reaction was terminated when the residual isocyanate group became 0.1% or less, and a composition containing a urethane acrylate compound was obtained (weight average molecular weight: 1,100, solution viscosity: 330 mPa·s / 60°C).

[0086] (Synthesis of (meth)acrylic polymer (B-1)) 500 g of toluene was charged into a 2 L four-necked flask and heated so that the internal temperature reached 80°C. Next, a mixture of 300 g (60% by mass) of methyl methacrylate, 200 g (40% by mass) of isobornyl methacrylate, and 1 g of azobisisobutyronitrile as a polymerization catalyst was added dropwise into the flask over 2 hours at a constant rate. The addition was carried out while stirring the inside of the flask and maintaining the internal temperature at 80°C. Thereafter, 0.2 g of azobisisobutyronitrile was additionally charged a total of 4 times every 1 hour, and the mixture was stirred at 80°C for 6 hours to produce a (meth)acrylic polymer (B-1). The weight-average molecular weight in terms of polystyrene measured by GPC was 40,000.

[0087] (Synthesis of (meth)acrylic polymer (B-2)) A (meth)acrylic polymer (B-2) was produced in the same manner as the synthesis of the (meth)acrylic polymer (B-1), except that the mixing ratio of the monomers to be added dropwise was 280 g (56% by mass) of methyl methacrylate, 110 g (22% by mass) of isobornyl methacrylate, and 110 g (22% by mass) of isobutyl methacrylate. The weight-average molecular weight in terms of polystyrene measured by GPC was 65,000.

[0088] (Glycerin (meth)acrylate (C-1) derived from biomass) EO-modified diglycerin tetraacrylate (product name "Light Acrylate DGE-4A") of Kyoeisha Chemical Co., Ltd. was used.

[0089] (Glycerin (meth)acrylate (C-2) derived from biomass) Glycerin triacrylate (product name "Aronix M-930") of Toagosei Co., Ltd. was used.

[0090] (Synthesis of urethane (meth)acrylate (D-1)) Into a flask equipped with an internal thermometer, a stirrer, and a cooling tube, 161.07 g (0.725 mol) of isophorone diisocyanate, 366.62 g (0.362 mol) of polytetramethylene ether glycol [BioPTMG1000; Mitsubishi Chemical Corporation, hydroxyl value: 110.9 mg KOH / g], 13.79 g (0.181 mol) of 1,3-propanediol, 0.40 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst were added, and the reaction was carried out at 65 °C. Then, when the residual isocyanate group reached 4.1% or less, it was cooled to 60 °C, 458.53 g (0.368 mol) of an acrylic acid adduct of dipentaerythritol [hydroxyl value: 45.0 mg KOH / g] was added, the reaction was carried out at 60 °C, and when the residual isocyanate group reached 0.1% or less, the reaction was terminated to obtain a composition containing a urethane acrylate-based compound (weight average molecular weight: 13,000, solution viscosity: 10,000 mPa·s / 60 °C).

[0091] (Synthesis of (F-1)) Into a flask equipped with an internal thermometer, a stirrer, and a cooling tube, 368.36 g (2.391 mol) of pentamethylene diisocyanate, 631.64 g (4.854 mol) of 2-hydroxypropyl acrylate (a25), 0.80 g of 2,6-di-tert-butylcresol as a polymerization inhibitor, and 0.04 g of dibutyltin dilaurate as a reaction catalyst were added, the reaction was carried out at 60 °C, and when the residual isocyanate group reached 0.1% or less, the reaction was terminated to obtain a composition containing a urethane acrylate-based compound (weight average molecular weight: 600, solution viscosity: 220 mPa·s / 60 °C).

[0092] Details of urethane (meth)acrylate (A-1) to (A-6) and (F-1) are shown in Table 1.

[0093]

Table 1

[0094] [Example 1] 19 parts by mass of urethane (meth)acrylate (A-2), 5 parts by mass of acrylic polymer (B-1), 17 parts by mass of biomass-derived glycerin (meth)acrylate (C-1), 17 parts by mass of urethane (meth)acrylate (D-1), 19 parts by mass of monofunctional acrylic monomer, 23 parts by mass of polyfunctional acrylic monomer, 4 parts by mass of 1-hydroxycyclohexyl phenyl ketone as a photoinitiator, and 0.32 parts by mass as an additive were mixed and dissolved to prepare an active energy ray-curable composition. Then, it was spray-coated onto a rectangular sheet substrate made of ABS resin with a length of 9 cm, a width of 5 cm, and a thickness of 3 mm so that the film thickness of the cured coating film would be 12 μm. Next, the organic solvent was volatilized by heating at 60 °C for 2 minutes using an oven. Then, in the air, using a high-pressure mercury lamp from above the coated surface, ultraviolet rays with an integrated light quantity of 1000 mJ / cm 2 (ultraviolet integrated energy amount with a wavelength of 340 nm to 380 nm) were irradiated to cure, and a laminate having a cured coating film that is a cured product of the active energy ray-curable composition was obtained.

[0095] [Examples 2 to 12, Comparative Examples 1 to 3] Except for changing the composition as shown in Table 2, the active energy ray-curable compositions of each example were prepared by the same method as in Example 1. Then, laminates of each example were obtained by the same method as in Example 1.

[0096] [Evaluation Method] (Appearance of Coating Film) The appearance of the coating film was visually observed, and the appearance of the coating film was evaluated according to the following evaluation criteria. A: No abnormality. B: There is whitening in a part of the coating film. C: There is whitening in most of the coating film.

[0097] (Adhesion) On the surface of the cured coating film formed on the surface of the ABS resin substrate, 11 cuts were made at intervals of 1 mm vertically and horizontally so as to reach the substrate, thereby forming 100 squares. After attaching a tape on the 100 squares, the adhesive tape was rapidly peeled off. After a total of 3 operations of peeling after attaching the tape were carried out, the state of the coating film was observed. The adhesion was evaluated according to the following evaluation criteria. A: Among 100 squares, 91 to 100 squares remain. B: Among 100 squares, 71 to 90 squares remain. C: Among 100 squares, less than 70 squares remain.

[0098] (Scratch resistance) In an atmosphere of 23°C and 55% RH, a weight of 750 gf (per an area of 4 cm 2 was placed on #0000 steel wool, and the surface of the coating film of the laminate was rubbed 10 reciprocations with a Taber abrasion tester (manufactured by Toyo Seiki Seisakusho, Ltd.), and the difference in haze before and after the test was measured and evaluated according to the following criteria. A: The difference in haze before and after the test is 0 or more and less than 0.5. B: The difference in haze before and after the test is 0.5 or more and less than 0.7. C: The difference in haze before and after the test is 0.7 or more.

[0099] (Decorative property) On the surface of the cured coating film formed on the surface of the ABS resin substrate, foil (FINEFOIL TA-5 Gold) was pressed at 160°C for 0.5 seconds with a desktop foil stamping machine. A cellophane tape was attached and peeled off from above the foil decorated on the substrate. The area of the foil remaining on the surface of the coating film was observed visually. It was evaluated according to the following criteria. A: The remaining foil area is 90% or more and 100% or less. B: The remaining foil area is 60% or more and less than 90%. C: The remaining foil area is 0% or more and less than 60%.

[0100] [Table 2]

[0101]

Table 3

[0102] As shown in Table 3, in Examples 1 to 12, a cured coating film exhibiting good adhesion and decorativeness in addition to good scratch resistance was obtained.

Industrial Applicability

[0103] According to the present invention, there is provided an active energy ray curable composition capable of obtaining a cured coating film exhibiting good decorativeness in addition to scratch resistance.

Claims

1. An active energy ray-curable composition containing urethane (meth)acrylate (A) and (meth)acrylic polymer (B), wherein the urethane (meth)acrylate (A) has at least one structural unit (a1) selected from the group consisting of a structural unit based on 1,5-pentamethylene diisocyanate and a structural unit based on a derivative of 1,5-pentamethylene diisocyanate, and a structural unit (a2) based on (meth)acrylate, and the concentration of the (meth)acryloyl group in the urethane (meth)acrylate (A) is 5 mmol / g or more.

2. The active energy ray-curable composition according to Claim 1, wherein the content of biogenic carbon atoms in the structural unit (a1) is 50% by mass or more.

3. The active energy ray-curable composition according to Claim 1, further containing biomass-derived glycerin (meth)acrylate (C).

4. The active energy ray-curable composition according to Claim 3, wherein the glycerin (meth)acrylate (C) is glycerin di(meth)acrylate (C1).

5. The active energy ray-curable composition according to Claim 3, wherein the proportion of the (meth)acrylic polymer (B) is 30 parts by mass or more with respect to 100 parts by mass of the glycerin (meth)acrylate (C).

6. The active energy ray-curable composition according to Claim 1, further containing a urethane (meth)acrylate (D) having a structural unit based on the following compound (d1), a structural unit based on the following compound (d2), and a structural unit based on the following compound (d3). Compound (d1): An isocyanate compound having at least two isocyanate groups (excluding 1,5-pentamethylene diisocyanate). Compound (d2): At least one polyol selected from the group consisting of polyether polyol, polyester polyol, and polycarbonate polyol. Compound (d3): A compound having a hydroxyl group and a (meth)acryloyl group.

7. The active energy ray-curable composition according to Claim 6, wherein the compound (d3) is a compound other than glycerin (meth)acrylate.

8. A cured product of the active energy ray-curable composition according to any one of Claims 1 to 7.

9. The cured product according to Claim 8, wherein the content of biogenic carbon atoms is 10% by mass or more.

10. It has a base material and a cured coating film provided on the surface of the base material, The laminated body, wherein the cured coating film is composed of the cured product according to claim 8.

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